WO2016113486A1 - Method for storing and releasing energy by reduction and oxidation of aluminium particles - Google Patents

Abstract

Method for releasing and storing energy using metal particles, preferably made of aluminium, of size comprised between 2 nm and 800 µm, for releasing thermal energy and producing dihydrogen and carbon monoxide by oxidation of said particles in a spray possibly within an ionised gas plasma, and for storing energy by reduction of metal oxide, preferably alumina, into particles of metal, preferably of aluminium, of size comprised between 2 nm and 800 µm, said particles being kept in a liquid or gaseous storage medium, the particles being passivated either by an oxide layer or by the storage medium.

Description

 METHOD FOR STORING AND GENERATING ENERGY BY REDUCTION AND OXIDATION OF ALUMINUM PARTICLES

 Introduction

The storage of electrical energy remains one of the main challenges in alternative renewable energy production methods, particularly solar and wind. Indeed, in these modes of production, the solar or wind resource is generally not in phase with the energy demand. There is the problem of efficiently storing energy.

This problem is the same for electric vehicles that have to store electricity with high efficiency.

 Of the storage modes, storage of chemical energy in batteries is the most used, however the least expensive traditional lead batteries are highly polluting and have low conversion efficiencies. In addition, the performance of these batteries falter on use. More efficient batteries using rare elements are increasingly used, but these batteries are very expensive, and their production and recycling very polluting. The world reserves of rare elements used in the manufacture of these batteries do not make it possible to envisage a use for the storage of energy at the level of a population, or even for the storage of the electrical energy of a vehicle. the planetary scale.

 A new type of energy storage in molten salts is currently used for solar power plants, although it is an interesting alternative to traditional storage in batteries, this storage method is limited to thermal technologies and has a low conversion efficiency . In addition, the facilities are large and difficult to miniaturize.

 The storage of electrical energy by the production of hydrogen, which will subsequently be burned in turbines or engines to produce electrical or mechanical energy, or converted into electrical energy in fuel cells, seems to be one of the most effective solutions. promising for the storage of energy, especially renewable. Nevertheless, the production of dihydrogen and the storage of it still remain problematic.

 Most of the dihydrogen produced in the world comes from the use of oil, which does not make it a renewable energy for the moment.

 A first solar plant in Corsica stores electrical energy in hydrogen by electrolysis of seawater. This hydrogen is used later to produce electricity on demand through a fuel cell.

 In addition to the poor conversion efficiency for electrolysis, there is the problem of hydrogen storage on a large scale, the hydrogen molecule being extremely small, most reservoirs designed to store it leak more or less long term, which partly explains the low development of hydrogen technologies.

New forms of storage of hydrogen are being developed, especially solid in the form of alkali metal hydride such as Mg or Na.

But these compounds do not reduce the danger of hydrogen, in fact, the hydrides are often pyrophoric, and hydrogen gas is itself extremely flammable.

A possible solution for the use of hydrogen would therefore be to prepare extern externally, from water for example ^ just before use.

The energy required for the production of hydrogen is provided by an oxidation-reduction reaction, for example with an alkali metal such as Mg, Na, K, etc., the oxidized metal being subsequently regenerated, for example from a laser very energetic, this hypothesis was imagined in the context of the solar laser project developed to regenerate magnesium oxide.

However, alkali metals do not lend themselves to the storage of energy because of their dangerousness and extreme reactivity.

On the other hand, aluminum with a redox potential of 1.61 could be a good candidate because it is much less reactive. But aluminum, which is very reactive with water or oxygen in the air, is quickly passivated by a layer of alumina A1203 10 nanometers thick. This property makes it difficult to deeply oxidize the aluminum object and thus recover all the redox energy. On the other hand, the energy required to regenerate the aluminum by reduction by the conventional electrolysis techniques of A1203 alumina is 13.5 MWh / ton because of the losses by Joule effect, whereas in theory it should not to be only 5.56 MWh / ton.

 To circumvent these problems limiting the use of aluminum as a support for storing and producing energy, we propose a process that allows, on the one hand, the more complete oxidation of aluminum by operating this oxidation on particles. of aluminum, and under the action of an excitation such as high frequency or microwaves, this oxidation possibly occurring within an ionized gas plasma, and secondly to operate the reduction of Alumina in a gas plasma, subjected to at least one electric and / or magnetic field for sorting the positive aluminum ions from the other plasma ions.

 The process will take advantage of plasma ion propulsion systems to produce and sort aluminum ions. The process can be applied to other metals than aluminum to obtain a reduced metal.

 1) The method comprises, in a first step, on the one hand the generation of a spray of metal particles typically of aluminum constituting the reducing phase, such that the size of the particles is preferably between 2 nm and 800 μm. and secondly, a spray gaseous or liquid oxidant constituting the oxidizing phase, preferentially water, CO 2 or a mixture of these two compounds. At least one of the two phases will be activated by an excitation means such as electromagnetic irradiation, such as laser radiation, solar radiation, microwaves, radio frequency, high frequency electric field, magnetic field varying at high frequency. frequency or any combination of these excitation means. The activation of the at least one phase may go as far as to reach the formation of a gas or a plasma such that the oxidation of the metal is complete and in particular the oxidation of aluminum to alumina.

When the oxidizing phase is H20

the expected reaction is

 2 Al + 3 H20 → A1203 + 3 H2

 When the oxidizing phase is C02

The expected reaction

is

 2 Al + 3 CO 2 → Al 2 O 3 + 3 CO

 In the plasmas recombinations can be done at the elemental level of Al, H, O, C or ions or equivalent radicals present in the plasmas.

 The particle spray can be obtained using a rare gas such as argon, xeon, kripton. In some embodiments, the particle spray will be made with the oxidizing gas such as CO 2, H 2 O, CO, water vapor, a mixture of these gases, or from a suspension in water of the metal particles. . In these particular cases, a single spray mixing the oxidant and the reducing agent can be used. In other embodiments, the particle spray will be obtained from CO 2, while the oxidizing phase will comprise a spray of water or water vapor, possibly CO, the water being five times more reactive than CO 2 oxidation will then occur essentially by water.

2) The method comprises, in a second step, the generation of a spray of particles of metal oxides typically of alumina, activated in plasma by a means such as electromagnetic irradiation, laser radiation, solar radiation, microwave, radio frequency, high frequency electric field, high frequency magnetic field, interaction with electrons or any combination thereof. The activated elements are then subjected to electric or magnetic fields or a combination of these fields, so as to separate the positive ions from the rest of the elements of the plasma or the mixture of elementary particles, possibly to separate the negative ions from the other elements of the plasma. or a mixture of elementary particles.

 The spray of particles of metal oxides, typically alumina, will be obtained with a neutral gas such as argon, kripton. the use of argon has the advantage of facilitating plasma formation by virtue of its plasmagenic properties.

 3) In a particular embodiment, the reactor of the first step comprises a FIG. 11 tube made of quartz, ceramic or any other material permeable to microwaves or to the electric and / or magnetic field, such as silicon carbide, nitride boron, zirconium, peek ect, of diameter between 1 cm and 50 cm preferably of diameter less than 6 cm. At the base of the tube is a Figl .2 device for injecting a spray of metal particles, typically aluminum particles between 2 nm and 800 μνη. It may be a simple nozzle, the particle spray may be obtained using a neutral motor gas such as argon. In a particular embodiment, the gas may be CO.sub.2. In some embodiments, a liquid oxidant spray, such as water, is introduced by the same nozzle FIG. In other embodiments a second nozzle may be used for the oxidizing phase, this oxidant may be CO 2, CO or water vapor or a water spray. In other embodiments, water vapor CO or CO 2 may replace argon as the driving gas. Different variants may use any mixture of these gases.

 4) in a particular embodiment, the quartz or ceramic tube crosses perpendicularly at least one waveguide Figl .3, at the ends of which is fixed at least one microwaves generator Figl .4 or magnetron such as micro emitted waves pass through the waveguide forming the excitation device. The microwaves used may have any value in the range of microwaves from 1 to 300 GHz. The waveguide may advantageously be replaced or supplemented by a downstream 3 comprising adjusting pistons. The gases and particles passing through the waveguide undergo a heating vaporizing the materials, until possibly transforming them into plasma thus allowing the complete oxidation of the metal by oxidants such as CO 2, H 2 O, optionally CO and the reduction of the oxidants, depending on the oxidant used in H2 hydrogen, carbon monoxide CO possibly carbon and a very large amount of heat that will be evacuated in the gases produced or in the engine gases used to make the sprays. The heat of the gases can be recovered to produce energy (electrical, mechanical ect), the gases produced can be turbined or used as for Η2 in fuel cells or for other industrial uses. When the CO 2 is used as an oxidant, the addition of steam or a water spray through a venturi (vacuum generator) Fig. 5 disposed for example after the waveguide, can produce of the dihydrogen by the following reaction /

 CO + H20 → C02 + H2

 When carbon monoxide is used as oxidant

3CO + 2A1 → A1203 + 3C

the carbon produced can be used as fuel or can be used in industry

5) in some embodiments the at least one waveguide and the at least one magnetron will be completed or replaced by at least one solenoid enclosing the tube connected to a high frequency generator and for injecting a high frequency varying magnetic field in the frequency tube between 10 Hz and 1GHz. The metal particles allow the spontaneous ignition of plasmas.

 In some embodiments, a quartz or ceramic tube Fig. 6 comprises a second quartz or ceramic tube Fig. 7 such that the tube Fig. 7 extends beyond both sides of the tube Fig. 6. One of the ends of the tube Fig. 6 is closed by a wall Fig. 8 which joins the wall of the tube Fig. 7. At or near this wall is arranged the injection point of the oxidizing and reducing phases such as nozzle or any other injection means. In some embodiments, the injection is through a venturi (vacuum generator) Figl .9 whose holes are directed down Figl .10 and arranged at the end of the tube Figl.6. At the other end of the tube Fig. 6 is arranged a system of fins or blades Fig. 11, causing the gases, sprays or plasmas relaxing in the tube Fig. 6 to adopt a vortex flow passing through said vanes or fins. The tube Fig. 6 passes through an excitation device such as a high frequency generator, a waveguide F1, 1.3 and microwave, and the like. The tube Fi l.6 continues after the blades by a tube ending in a cone Figl .12. The tube Figl .7 continues beyond the blades or fins to the first third of Figl tube 12 ending in a cone, the latter forming a cyclone. In the FIG. 7 tube is arranged a Figl ceramic filter 13 capable of capturing alumina particles, for example with pores of 2 nm in diameter.

When the oxidizing and reducing phases are injected into the FIG. 6 tube while passing through the excitation device, the reducing agents and / or oxidizing agents are optionally activated until a plasma is formed which causes the oxidation of the metal, typically aluminum, to become alumina. The already formed gases, plasmas and oxide particles or non-vaporized or non-oxidized metal particles are vortexed into the conical tube Fig. 12 through the blades Fig. 11. At the bottom of the conical tube Fig. 12, a column of ascending gas is formed, captured by the tube Fig. 7, the larger particles are trapped at the bottom of the cone of the tube Fig. 12. The rising gas whose composition depends on the oxidizing phase and the driving gas (H2, CO, He, argon, engine gas, etc.), captured by the cyclone outlet tube Fig. 7, and filtered by the filter Fig. thus eliminating all particles larger than the filter's pores. By crossing the excitation device again the unoxidized aluminum metal can be further oxidized. The dihydrogen and / or carbon monoxide which again pass through the excitation device will again be heated by the microwaves or the varying field and will form a plasma to remove any remaining stainless particles transported with the rising gas.

The redox reaction is highly exothermic, particularly the reactions between H 2 O and Al but also between CO 2 and Al. Once initiated, these reactions self-maintain. The gas rising in Fig. 7 will absorb the excess heat to regulate the temperature of the reactor. In some embodiments, the motor gas, or the oxidizing phase, or both, circulates in at least one exchanger Fig. 14 disposed at the conical tube Fig. 12, before being sent into the injection device.

 This exchanger makes it possible to cool the vortex gas before it rises and to preheat the oxidizing and / or reducing phase. Additional exchangers for example water can be arranged at the conical tube Figl .12 to recover the heat at this level in the form of steam for example. This steam can be used to produce heat or cold.

7) In a particular embodiment the tube Figl.6 is replaced by two nested tubes Figl .15 and Figl .16, an annular surface Figl .17 connecting a tube end Figl .15 to the wall of the tube Figl. that the walls of the tubes Figl.15 and Figl .7 form an annular chamber. A circular wall 18 connects the other end of the tube Fig. 15 to the contiguous end of the tube Fig. 16 so as to close the space between the two tubes. The means for injecting the oxidizing and reducing phases are disposed on this wall FIG. 18 or at the level of this wall when it is a matter of venturi (vacuum generator) FIG. 9. For the latter solution the venturi holes (vacuum generator) are directed upwards. A system of fins or vanes connects the end of the tube Figl .16 to the wall of the tube Figl .7 to define the entry Figl .11 of the vortex cyclone formed by the tube Figl .12. The nested tube system can be repeated several times to form a tube circuit annular winding through the means or excitation device.

 8) In a particular embodiment of the energy storage step by the reduction of the metal oxide typically alumina aluminum, the reactor comprises a quartz tube, ceramic or other material permeable to micro or electromagnetic field and / or magnetic Fig2.1 such as silicon carbide, boron nitride, zirconium, peek etc, with a diameter of between 1 cm and 50 cm, preferably less than 6 cm in diameter. At the base of the tube is arranged a device for injecting Fig2.2 a spray of metal oxide particles, typically alumina particles between 2 nm and 800 μπι. It may be a simple nozzle, still a venturi system (vacuum generator). The particle spray can be obtained using a neutral motor gas such as argon, xenon, kripton, helium or dihydrogen. In a particular embodiment, the engine gas may be supplemented with a cladding gas, for example argon, helium or dihydrogen FIG. The tube passes through at least one plasma excitation device FIG. 2.3.4, such as microwaves, high frequency electric or magnetic field, electronic excitation, electromagnetic radiation, etc., for example the plasma excitation device. waveguide and magnetron, such as the tube passing through said excitation device, a plasma is ignited from the spray of particles and gas. To allow the plasma to be more easily ignited, is added to the metal oxide spray such as alumina, a percentage of already reduced metal particles such as aluminum particles. Preferably, the percentage of aluminum particles will be less than 10%. Under the excitement the metal particles will ignite the plasma. After the excitation device, the tube bifurcates to form a Y Fig2.19. On each branch of the Y is disposed a hollow electrode preferably forming a pierced inverted cone. One of the electrodes is connected to the positive pole of a generator to form an anode Fig2.20, the other is connected to the negative pole of a generator to form a cathode Fig2.21, for example a potential difference of 15 kV will be maintained between the two electrodes, this potential difference will preferably be adjustable as a function of the plasma temperature and the gas velocity. After spraying the spray with gas and ionizing said plasma gas, the positive ions or cations such as A13 + will be attracted to the hollow cathode and pass through it. At the passage of the cathode, these ions will eventually be able to capture an electron to produce a reduced metal such as Al. Negative ions typically O- will be attracted to the hollow anode and will pass through it, passing the negative ions will give an electron to the anode and will be able to recombine in compounds such as 02. The engine gas or cladding such as argon, xeon, helium, will be ionized also, being particularly inert, these elements will be neutralized simply to the electrodes. In order to better filter the ions two magnetic tori, such as a coil wound around a ring Fig2.22 or wound in a vortex, may be arranged upstream of each electrode. The current flowing in the coil upstream of the cathode will be such that it will generate a magnetic field causing the positive charges to pass through the center of the torus or magnetic vortex and driving back the negative charges. Conversely, the current flowing in the coil upstream of the anode will be such that it will generate a magnetic field causing the negative charges to pass through the center of the torus or magnetic vortex and driving back the positive charges.

Downstream of each electrode will optionally be arranged a metal gate through the conduit at the same potential as the electrode Fig.2.23, this grid can neutralize the elements that have not been by the electrode.

 Undesirable reactions can occur at the cathode including the presence of 0+, O., or H + if there is use of dihydrogen. These elements may generate undesirable interactions with the aluminum formed and oxidize a portion of it to alumina. To increase the efficiency the output of the cathode can be connected to the input of an identical device so as to repeat the selection of positive ions Fig.2.24.

9) In a particular embodiment of the reactor of the step of reducing the metal oxide, a positive annular electrode Fig2.25 is disposed at the injection level of the metal oxide sprays and a transmitter of electron such as an electron gun Fig2.26a, a THT, injects electrons into the plasma or around the plasma. In other embodiments, the electron guns 26b are disposed at the level of the injection of the spray so that the electron jet passes through the plasma.

 In some embodiments, the spray additionally comprises particles of alumina, particles selected from sodium fluoride NaF crystals (5 to 10% by mass) of 2 nm to 800 μm, KF potassium fluoride crystals (5 to 10% by weight), at 10 mass%) of 2nm at ΒΌΟμνη, aluminum fluoride crystals A1F3 (5 to 10% by mass) of 2 nm to 800 μm, cryolite particles Na3AlF6 of 2 nm to 800 μm, crystals of sodium chloride NaCl (5 to 10% by weight) from 2 nm to 800 μm,

Crystals of aluminum chloride A1C13 (5 to 10% by mass) from 2 nm to 800 μm, carbon particles from 2 nm to 800 μm.

 The fluoride and / or chloride anions provided to the plasma aid in the decomposition of AI203 to A13 + and O-. The sodium or potassium cations collected at the cathode at the same time as the A13 + make it possible to improve the reduced Al yield in particular by capturing the 0+.

 11) In some embodiments argon is supplemented with dihydrogen and / or helium

12) In some embodiments, the alumina is mixed with any combination of NaF, KF, AlF3, AlCl3, Na3AlF6, NaCl, C in proportions ranging, for example, from 0 to 50% by weight. The mixture is mounted at a temperature above 950 ° C, to obtain a heterogeneous molten salt or a heterogeneous partially fused salt.

 Then the liquefied mixture is sprayed into the reactor of the reduction step of

The metal oxide.

 The preheating may be performed by induction, by the action of a magnetic or electric field varying at high frequency, by the convection of solar radiation or by a combination of these means.

 13) In a particular embodiment of the reactor of the step of reducing the metal oxide, typically aluminum alumina, after the plasma excitation device Fig. 2.3, the reactor tube forms a cross fig2.27. At each horizontal branch of the cross, is disposed a hollow electrode fig2.20-21 forming for example a pierced inverted cone. Possibly upstream of each electrode is arranged a magnetic torus

Fig.2.22 such as a coil wound around a ring or wound in a vortex and possibly downstream of the electrode a gate connected to the electrode Fig.2.23. In some embodiments the two branches of the cross can be raised to form a Y Fig5.27. From the cross Fig.2.27, Fig5.27 the reactor tube is continued. After the formation of the plasma at the level of the excitation device, the positive ions will be attracted by the cathode and

40 possibly the torus upstream of said cathode, the negative ions will be attracted by the anode and possibly the torus upstream of said anode. The neutral elements will continue their course in the extension of the high part of the cross forming the conduit of the neutral elements Fif2.28, Fig5.28. The charged ions can be neutralized during their passage in the hollow electrodes, or by their passage in the grids

45 placed downstream of said hollow electrodes. In some embodiments of the electron guns disposed downstream of the hollow electrodes 26 may inject electrons into the conduit of the cross arm downstream of the hollow electrodes to neutralize the species.

 In a particular embodiment the duct of the neutral elements 28 curves and continues to be connected to the input of an electric or magnetic thruster, any type of electric or magnetic thruster may be suitable, for example we will describe the case of a Hall effect thruster Fig2.29, Fig5.29.

 Different Hall effect thruster complexities exist, for the purposes of description 55 a single thruster has been chosen, but other more complex thrusters may be suitable.

The Hall effect thruster comprises two interlocking ceramic cylinders Fig.3.30-31. Any kind of ceramic permeable to a magnetic field or an electric field may be suitable without being exhaustive, boron nitride, zirconium, silicon carbide, etc. In a preferred embodiment the outer cylinder Fig. 3.3 will be the wall of the conduit of the neutral elements. Inside the innermost ceramic cylinder Fig3.30 is arranged a winding Fig3.32 and outside the outermost cylinder is disposed another winding Fig3.33 such that when said windings are traversed by an electric current , they generate a radial magnetic field between the intra and extra cylinder windings. At the bottom of the inter-cylindrical space is disposed an annular anode Fig3.34 pierced with holes. This anode represents the entrance of the Hall effect reactor. An optionally hollow cathode Fig3.35 is set back from the outer cylinder. A tapping and a bifurcation of the neutral elements conduit allow the implantation of said cathode. Part of the electrons ejected from the cathode move towards the anode and are trapped by the lines of the magnetic field around which they wind and make them travel between the two cylinders. Some of these electrons follow a path that takes them from field line to field line, thus forming the hall currents. The electrons traveling between the two cylinders and the Hall electrons will generate shocks with the aluminum atoms from the plasma, but also with residual molecules or possibly alumina particles from the plasma produced by the excitation device of the plasma. plasma. Indeed, during their passage in the plasma alumina particles are reduced to neutral or ionized elements, however there may remain in the plasma alumina molecules or incompletely vaporized particles. Shocks with electrons in the Hall reactor will ionize atoms and alumina molecules, impacted alumina molecules will tend to decompose. The cations formed will be expelled out of the Hall booster by the electric field of the anode, a number of cations will be neutralized and continue a straight race, unneutralized cations will be diverted to the hollow anode Fig2.36. In a particular embodiment, an electron gun will generate the electrons Fig3.37 of the Hall thruster, for ionization and a hollow cathode possibly cone Fig3.36 will form a cation trap preferably disposed at 180 ° or 90 ° of the electron gun. The electron gun may include a THT of 15KV. Upstream of the hollow cathode forming the cation trap Fig. 2.36, Fig. 3.3, a torus Fig.2.22, Fig. 3.22 such as a winding wound around a cylinder or in a vortex will be disposed in front of the trap electrode 36 The current flowing in the torus will be such that it leads the cations to pass through the center of the torus and repels the anions or electrons. In a particular embodiment, downstream of the capture electrode may be arranged a Fig3.23 grid and possibly a second electron gun to neutralize the cations.

 The ionization will reach not only the metals such as Al but also the driving gases and oxygen brought by the oxide. Only cations will be ejected from the Hall Booster, possibly A13 +, Ar +, 0+ possibly H + if present. Argon being a noble gas it will neutralize itself without reacting, on the other hand A13 + and 0+ after neutralization, can react one on the other. However, since O is much more electronegative than Al, the production of 0+ will be minimized relative to that of A13 +, and 0+ will be neutralized much faster than A13 + allowing time to collect A13 + at the hollow capture electrode of cations.

 14) In a particular embodiment of the reactor of the reduction step of the metal oxide, typically aluminum alumina, after the formation of the different plasmas, the neutral elements at the output of the excitation means and / or electric thruster or / and -magnetic-will be returned to the plasma generating device Fig2.A so as to generate a loop through a curved conduit Fig2.37, Fig5 which opens for example in the input of a venturi (vacuum generator) Fig2.9 disposed below the excitation means.

 15) in some embodiments the reduced aluminum capture conduits may be connected to the inlet of a second reactor of the metal oxide reduction step for a second reduction / selection cycle of the 'aluminum.

In a particular embodiment, the reduced aluminum capture ducts Fig4.38-39 come together in a single duct. The conduit leads tangentially to a cyclone Fig4.40 of diameter preferably between 1 and 20 centimeters in a material having a good thermal conductivity such as copper, silicon carbide, talium or any other compatible material to achieve a heat exchange. At the low end of the cyclone is a Fifty-four cock, the first third of the cyclone is

5 rising gas collection pipe Fig4.42. The cyclone is disposed in an exchanger chamber Fig4.43 in which a gas flows counter-sensitively, preferably argon Fig4.44. The temperature of the exchanger gas will be adjusted so that the aluminum is cooled to a temperature below 2000 ° C and above 660 ° C so as to liquefy it. The exit of the gas tube going back from cyclone Fig4.42 will be

Kept strictly between 660 ° C and 800 ° C; A ceramic filter with pores less than 2 nm Fig4.13 will for example be disposed at this outlet so as to force the liquefaction of aluminum. Temperature and level sensors will be introduced at the cyclone. When liquid is present in the cyclone the electric valve is open, a net of liquid aluminum will flow then. This net can be cast in ingot.

15

 16) In a preferred embodiment, the aluminum net flows on a ceramic plate maintained at a temperature of between 660 ° C and 700 ° C. The ceramic plate is connected to a piezoelectric cell, so as to generate ultrasonic vibrations, for example between 16 kHz and 10,000 kHz. In contact with the plate

The net is fragmented into micro-droplets and / or nano-droplets depending on the ultrasound frequency applied to the plate. An argon jet at 660 ° C expels the droplets from the plate, a second jet of cold argon carries the spray droplets cooling them.

 The nano-particles thus prepared are then stored in a container optionally in argon or water depending on the diameter of the particles.

 In another embodiment the valve opens into a pommel whose base is formed by a perforated ceramic plate maintained at a temperature of between 660 ° C and 700 ° C. The perforation holes will be between 2 nm and 200 μm by

Example. The plate of the ceramic knob is connected to a piezoelectric cell so as to generate ultrasonic vibrations, for example between 16 kHz and 10,000 kHz. By flowing through the holes the molten aluminum forms droplets that will be chopped at the frequency in nano or micro-droplets with a diameter of between 2 nm and 200 m. An argon jet at a temperature of between 660 ° C and 700 ° C

35 carries the spray droplets.

 The spray will be cooled by incorporating an argon jet at a temperature below 660 ° C.

 17) In some embodiments the aluminum capture ducts Fig4.38-39 40 joined in a single duct, or the cyclone valve Fig4.40, open into the longitudinal inlet of a venturi (vacuum generator ) Fig4.44 whose lateral arrival Fig4.45 is fed with argon between 660 and 700 ° C at a pressure between 1 and 150 bar. The suction generated by the venturi effect breaks up the liquid aluminum into droplets of 2 nm to 800 μm depending on the applied lateral pressure.

In some embodiments, the outlet of the venturi (vacuum generator) corresponds to the inlet of a second venturi (vacuum generator) e fed laterally by cold argon at a temperature below 660 ° C. so as to cooling the aluminum droplets in nano and / or microparticles with a size of between 2 nm and 800 μm ^η .

18) particle spray can be concentrated through a vortex tube. The particle spray at the outlet of a venturi will feed the lateral inlet of a vortex tube at a pressure of between 1 and 150 bar. The particles can be fractionated dichotomically by size limit between the hot gas outlet and the cold gas, the limit will depend on the inlet pressure and the adjustment of the vortex tube.

 55

19) In a particular embodiment, the nano or micro-particles of aluminum having a diameter of between 2 nm and 800 μ η will be stored in a storage medium such as argon in a metal container, polymer, composite, carbon, polyimide ect. In other processes nano or micro-particles of aluminum having a diameter between 50 nm and 800 μω will be stored in a storage medium such as liquid water in containers of the same kind as previously. Storage in liquid water or CO 2 will passivate the aluminum to a thickness of 10 nm with release of H2 or CO2 which will eventually have to be removed from the container. The particles passivated by a layer of alumina are less sensitive to oxidation and much more stable; however, to be completely oxidized it requires activation as described above to initiate the reaction. Other activations can be envisaged such as the electric arc produced for example by

10 electric candles or by flame. However, these activations do not guarantee complete oxidation of the particles as obtained with the methods presented in this invention. On the other hand, particles smaller than 40 nm stored in argon are passive in the storage gas. These so-called passivated particles by the storage gas are much more reactive, and can be completely oxidized by

15 simple exposure to oxygen, carbon dioxide or water with or without excitation.

 Other storage gases can be used such as most rare or noble gases, helium ...

 20) in a particular embodiment the storage of the particles will be carried out in a container having two compartments, a compartment Fig5.46 will include the particles for example stored in an argon gas at a pressure PI greater than atmospheric pressure, surrounded by a second container Fig5.47 comprising in space separating the two contaneur, D type extinguisher powder Fig5.48 pressurized

Also by argon. A valve Fig5.49 or a common lid tare to open or given at a certain pressure. In case of pressure on one of the two components, for example, excessive pressure buildup due to fire. the valves or lids yielding causing the mixture in a particle spray of metal and extinguishing powder D towards the outside avoid the explosion and combustion of

Aluminum.

21) In some embodiments a container Fig5.50 comprising a type D extinguisher powder will be placed in the container comprising the aluminum particles,

This container will have a valve or membrane or valve capable of opening if the temperature or pressure becomes too great in the compartment containing the metal particles such as aluminum particle, so that the powder of the type D and the metal particles can mix. In some embodiments, the walls of the container, including the type D powder, are not heat resistant, for example

For example, it will be made of a polymer that liquefies from a temperature of 90 ° C.

 22) In a particular embodiment, the central reservoir 46, included in the container containing a type D powder, comprises a movable piston Fig5.51 separating it in two.

45 The piston will have seals ensuring tightness between the two compartments.

 On one side of the piston the tank Fig5.52 will be filled with type D extinguisher powder and a gas such as argon guaranteeing a pressure P pushing for example 70 bar. On the other side of the piston the tank will be filled with metal particles such as aluminum in a gas such as argon or CO2 or in a hydraulic suspension or CO2

50 supercritical. The proportion between the amount of particles and gas or water will be defined so that the spray formed has a given particle density. In some embodiments a magnetic bar is introduced into the compartment comprising the metal particles in order to be able to create agitation in this compartment to homogenize the suspension or the particle / gas mixture. Valves or membranes of

In the case of a break or safety valves calibrated at a certain pressure, Fig. 5,53 are introduced into the piston, these devices are intended to break or open if the pressure becomes too great in at least one of the compartments on the one hand or on the other. piston, so that the D-type powder and the metal particles mix. The The structure of the reservoir is designed to deform in the form of a sphere beyond a certain internal pressure so that the contents of the two compartments can mix.

 The containers described herein provide a solution for storing and transporting metal powders so that they can be used in fuel, for example in the processes described herein while overcoming the risk of metal fire particularly important for aluminum particles. Indeed, the double shell that represent the two nested tanks can neutralize the flammable power 10 of a particle spray in case of piercing the tank. Indeed, the reservoir containing the type D powder will be pierced first, and the type D powder will mix with the metal spray.

 In the case of an overpressure due to heating of the containers, before the rupture of the container, the safety valves Fig. 5.49, will release a spray of a mixture of powder type D and metal particles.

 The described piston reservoir makes it possible, on the one hand, to control the ejection pressure of the metal spray independently of the gas / particle or water / particle formula of the tank containing the metal particles and it also makes it possible to provide a additional safety in case of overpressure in the tank, or piercing of the tank.

 20

 23) in some embodiments of the reactor of the metal oxide reduction step the Fig2.A-B devices will be in series such as AAA BBB or AB AB or in any combination. Under these conditions, the particle spray may be composed of heterogeneous particles of a mixture of particles of different metal oxides, or even of different metals. The temperature of the plasmas and the different electric fields of each stage A or B can be adjusted so as to generate the ionization of specific elements for each stage, and the selection of specific ions for sorting the elements in a mixture of oxide of metal or metal.

 18) In a particular embodiment, an infrared or ultraviolet light beam will be converged at the center of the reactor in the plasma excitation zone through a window Fig. 2.54 so as to have a dual source of light. excitation and heating of the plasma, under these conditions the reactor tube will be quartz or sapphire.

 In other embodiments, concentrated solar radiation conditioned by

For example, in a fiber optic or circular waveguide made of chromium, chromium-plated tantalum or chrome plated ceramic will guide the sunlight to the center of the reactor.

LEGENDS OF ALL FIGURES

D reactor tube made of quartz, ceramic or any other material

2) Device for injecting a spray of metal particles, nebulizer, nozzle etc. 3) downstream or waveguide

4) microwave

5) venturi (vacuum generator)

6) outer tube made of quartz or ceramic

7) Internal quartz or ceramic tube

8) wall closing the end of the tube 6 and which joins the wall of the tube 7

9) injection venturi (vacuum generator)

10 direction gas venturi (vacuum generator)

11 system of fins or blades

12 tube ending with a cone forming a cyclone

13 Particulate filter

14 heat exchanger

15 outer tube fitted

16 inner tube fitted

17 annular surface

18 sheathing gas

19 reactor Y-bifurcation

20 hollow anode preferably forming a pierced inverted cone

21 hollow cathode preferably forming a pierced inverted cone

22 magnetic toroid, such as a coil wound around a ring or vortexed 23 grid downstream of each electrode at the same potential as the electrode

24 tandem metal oxide reduction device

25 positive annular electrode

26 26a, 26b, electron gun

27 reactor tube forming a cross

28 leads neutral elements

29 Hall effect thruster

30 cylinder ceramic propellant with internal Hall effect

31 ceramic cylinder propeller with external Hall effect

32 internal coil winding Hall effect thruster

33 coil outer cylinder propeller Hall effect

34 annular anode pierced with holes

35 Hall effect reactor cathode

36 electron gun

37 curved conduit

38 reduced aluminum capture duct

39 reduced aluminum capture duct

40 cyclone

41 cyclone valve

42 Hurricane gas collection pipe

43 exchanger enclosure

44 longitudinal inlet of a venturi (vacuum generator)

45 Lateral arrival of a venturi (vacuum generator)

46 compartment particles

47 fire extinguisher powder compartment type D

48 type D fire extinguisher powder

49 valves or covers tared to open or give in at a certain pressure

50 container with a type D extinguisher powder

51 movable piston

52 part of the tank filled with pressurized D type extinguisher powder valve, diaphragm rupture, calibrated safety valve, at a certain pressure) Hublot

) Purge

Claims

 1) A process for producing and storing energy, characterized in that it consists in using metal nanoparticles with a size of between 2 nm and 800 μm to produce energy, dihydrogen and carbon monoxide, oxidation of the metal particles and for storing energy by reducing the metal oxide to metal preserved in the form of particles of size between 2nm and 800 ηι. 2) Process according to claim 1, characterized in that the production of energy, of dihydrogen, of carbon monoxide, is obtained by oxidation of aluminum particles in a spray, by an oxidant such as H 2 O, CO 2, CO, initiated and optionally activated in plasma by means such as electromagnetic irradiation, laser radiation, solar radiation, microwaves (Fig. 1.3), radio frequency, high frequency electric field, high frequency magnetic field, electric discharges.  3) Process according to claim 1, characterized in that the storage of the energy consists in reducing alumina to aluminum particles by vaporizing the alumina in the form of a spray in a gas plasma, preferably argon plasma-activated helium by means such as electromagnetic irradiation, laser radiation, solar radiation, microwaves (FIG. 2.3), radio frequency, high frequency electric field, high frequency magnetic field, electric discharges, to isolate the A13 + ions of the main plasma (20-21) and to reduce these A13 + ions by addition of electrons from electric cathodes, electron guns (Fig2.3).  4) Process according to any one of claims 1 and 3 characterized in that the aluminum, optionally mixed with at least one of the compounds NaF, KF, AlF3, AlCl3, Na3AlF6, NaCl, C, is brought to a temperature above 950 ° C before being sprayed into a spray to make a plasma.  5) Device set up to carry out the method according to claims 1 to 2, characterized in that it comprises nested tubes allowing a gas, a particle spray, a plasma to flow by winding (6, 7, 15, 16, 17) in an excitation source such as a high frequency generator, electromagnetic irradiation, laser radiation, solar radiation, microwave, radio frequency, high frequency electric field, high frequency magnetic field, electric discharges. 6) A device set up to carry out the method according to claim 5, characterized in that it comprises a cyclone (12,7) and optionally particulate filters (13), said cyclone making it possible to return (7) the gas for passing through the excitation source at which the oxidation reaction of the particles is carried out in order to cool this zone and to superheat the gas.  7) device set up to carry out the method according to any one of claims 5, 6, characterized in that it comprises a bifurcation such that, Y (19), cross (27). said bifurcations being provided with means such as electrodes (20, 21), a magnetic coil (22), a magnetic vortex capable of constraining the trajectory of charged elements such as cations, anions, electrons, in order to extract said elements from a plasma. 8) A device set up to carry out the method according to any one of claims 5, 6, 7, characterized in that it comprises means for injecting electrons into a reactor (1, 31) such as barrels to electrons (26). 9) Device according to any one of claims 5, 6, 7, 8 characterized in that it comprises at least one plasma excitation device and at least one electric or magnetic thruster such as a Hall effect thruster (29). , Fig. 3). 10) Device set up to carry out the method according to any one of claims 5, 6, 7, 8, 9, characterized in that the metal oxide spray reduction reactor, comprises at least one device for carrying out sprays of droplets of liquid metal such as cyclone, ceramic plate optionally perforated with pores connected to piezoelectric devices, venturi tube, at least one device for cooling said liquid metal sprays in sprays of metal particles of size between 2 nm and 800 / im such as venturi tube, vacuum generator (Fig4.5) and optionally at least one device for concentrating the particles such as vortex tube.  11) A device set up to carry out the method according to any one of claims 5 to 10, characterized in that the particles are stored in tanks, containers, ensuring the passivity of the particles for the storage medium while maintaining the reactivity of the particles, such as passivity, is obtained by a layer of alumina of 5 to 20 nm covering the aluminum particles from 50 nm to 800 ηι in H 2 O, by storage in a noble gas such as argon, 'helium.  12) Device according to claim 11, characterized in that the tanks, the containers, comprise a powder type D (48) disposed in parts of said tanks or containers, separated from the metal particles and their storage medium (46). , 47) such that said parts comprise means for mixing the metal particles and the type D powder before or during the breaking or piercing of the walls of said tanks or containers and such that the parts of said tanks or containers separated from the particles of metal comprise at least one of a nested double shell (46, 47), a pressurized gas, a safety valve (49), a tapered diaphragm, a valve, a movable piston (51, 53) , a wall capable of breaking at a given pressure or temperature below the rupture threshold of the materials of the walls of the container.